Nu, nu&#39;-bis (4-cyclohexylcyclohexyl) alkyl-idenediamines



nited States Patent "cc 1 1 2,838,568

Patented June 10, 1958 times precipitates in the reaction mixture as acrystalline 2838 568 solid. Upon completion of the reaction, thereaction mixture may be cooled to precipitate the desired productN,N'.BIS(4-CYCLOHEXYLCYCLOHEXYQALKYL- or to precipitate further product.The precipitate con- IDENEDIAMINES 5 veniently may be separated inconventional manner such as by filtration or decantation and thereafterpurified by i g gggfi g gggg: gffiiff t grz ggg recrystallization fromsuitable organic solvents.

of Delaware The (bicyclohexyl)-4 -amine employed as a starting materialIn the present invention occurs in two lsomeric No Drawing. ApplicationMay 6, 1957 forms known as the alpha and beta isomers. These two Sena!657,046 isomers may be prepared by known methods. In such 3 Claims (CL260 563) methods, 4-cyclohexylcyclohexanol is dehydrogenated over acopper catalyst at 300 C. to form 4-cyclohexylcyclohexanone, and thisproduct thereafter ammoniated The present invention is concerned withN,N'-bis(4- to form a Z-cyclohexylcyclohexanone imine. The lattercyclohexylcyclohexyl)alkylidenediarnines having the foris thereafterhydrogenated over a nickel catalyst at 60 C. mula and 75 pounds pressureper square inch to give a reaction GE -CH 01124311 CH3CHI GHQ-CHI e gCH-C CHNH-CHNHC 011-4311 0H,

CHE-"C 2 v GET-CH2 oo -R one-CH}; CH2 G t In this and succeedingformulae, R represents hydrogen, mixture containing about equal amountsof the alpha and chlorine, chloromethyl, chloroethyl, methyl, ethyl orbet/a isomers of (biCYCIOPeXYDA'Bmme' The 1 h d all-i rd chloride saltof the beta isomer of the .amine is soluble 1n Pmpy T compoun 5 f crystBe So 1 S i chloroform while the hydrogen chloride salt of the alphaWhat Soluble 111 y Organlc Solvents and Substantially isomer of theamine is substantially insoluble in chloroinsoluble in water. They havebeen found to be useful 8 T f tth l l g s m segaglted l t e orm o err yrogen c on e sa ts, an e sa ts as arasltlcfdes are adapted to i f asacuve thereafter converted to the free amine. The hydrogen toxlc nst t smedust and p y p s n for the chloride salts of the alpha and betaisomers of the amine control of the growth of many bacterial and fungalorganl at and respectively, isms such as Alternaria solani. Thecompounds are also Whlle the alpha lsomer of the amme melts at 58 andthe beta isomer of the amine melts at 32 C. useful as herbicides for thecontrol of the growth of seeds. The following examples illustrate theinvention but are The new compounds may be prepared by causing a 35notto be-construed as limiting:

' Example 1.-2,2,3-trichl0ro-N,N'-bi.s'-(4-cycl0hexylcycl0- hexyl-butylidenediamine tat-isomer Ont-CH, GE -OH, 011 011, GET-0H2 H2O CH-CCH-NH-(EH-NH-O CH-CH 0H,

polychloroaldehyde having the formula 2,2,3-trichlorobutyraldehyde (17.5grams; 0.1 mole) O dissolved in 100 milliliters of ether was slowlyadded porolkcf tionwise over a period of about 15 minutes to 36.2 grams(0.2 mole) of (bicyclohexyl)-4-amine ot-isorner dissolved i H in 200milliliters of ether. The addition was carried out 10 react POIUQHWISe YY with stirring and cooling and at a temperature of from reaction iscarried out in the presence of an Inert organic 20 to During theaddition, a 2 2 3 trichl r0. solvent such as ethanol, methanol or ether.Good results N,Nt bis(4 cyclohexylcyclohexyl) butylidenediamine areobtained when at least two molecular proportions of the amine areemployed with each molecular proportion of the polychloroaldehyde. Thereaction is somewhat exothermic and takes place smoothly within thetemperature range of from about 10 to about 70 C. with the isomerproduct precipitated in the reaction mixture as a crystalline solid. Thesolid product was separated by filtration, and recrystallized from apetroleum hydrocarbon having a boiling range of from -100 C. The

formation of the desired product and Water of reaction. recrystallizedProduct melted at and had The temperature may be controlled byregulating the rate a mtmgen Content f Percent as P t0 the of contactingthe reactants and by external cooling. calculated value of 5.63 percent.

Example 2.2,2,3-trichlor0-N,N-bis(4-cyclohexylcyclo hexyl)propylidenediamine a-isomer oat-out CHz-CH: GET-CH3 ant-on,

H3O on-c CH-NH-CH-NH-C o11-cn CH2 an -on, oHt-ofn' ron matron, orrz-chtIn carrying out the reaction, the polychloroaldehyde is In a mannersimilar to Example 1, 16.15 grams (0.1 contacted portionwise with the(bicyclohexyl)-4-amine in mole) of 2,2,3-trichloropropionaldehydedissolved in the reaction solvent and in the contacting temperaturemilliliters of ether is added portionwise over a period of range. Duringthe contacting, the desired product often- 30 minutes to 36.2 grams (0.2mole) of (bicyclohexyl)-4- amine a-isomer dissolved in 300 millilitersof ether. The sions, employed as sprays. In other procedures, theprodaddition is carried out with stirring and cooling and .at a net maybe employed as active toxic constituents of oiltemperature of from 30 to35 C. During the addition, in-water emulsions or water dispersions withor without a 2,2,3-trichloro-N,N'-bis(4-cyclohexylcyclohexyl)propyltheaddition of wetting dispersing or emulsifying agents. idenediaminea-isomer product precipitates in the reaction 5 In representativeoperations, substantially complete conmixture as a crystalline solid andis separated by filtratrols of tomato early blight (Alternaria solam')on tomato tion and dried. 2,2,3-trichloro-N,N'-bis(4-cyclohexylplantshave been obtained with the application of aqueouscyclohexyl)propylidenediamine ot-isomer has a molecular compositionscontaining 0.12 pound of 2,2,3-trichloro- Weight of 469.5.N,N-bis(4-cyclohexylcyclohexyl)butylidenediamine m-iso- Example3.--2,Z-dichZora-N,N'-bis(4-cyclohexylcyclohexyl) ethyliden ediaminea-isomer out-0H, 011F011! rim-011, CHI-CH} H1O 011-011 /CHNH-OHNHCHCHI-CH CH, \CEZCH1 \CHPCH2 C1101: CH CHz CH7-O 1 In a manner similar toExample 1, 11.3 grams (0.1 mer per 100 gallons of ultimate mixture tothe foliage of mole) of 2,2-dichloroacetaldehyde dissolved in 150millithe tomato plants. liters of ether was added por'tionwise over aperiod of I claim: minutes to 36.2 grams (0.2 mole) of (bicyclohexyl)-4-20 1. An N,N-bis(4-cyclohexylcyclohexyl)alkylidenediamine OL-iSOmI'dissolved in 200 milliliters of ether. The amine having the formula.

/CH1CH2 GHQ-CH: /CHg-CH1 GHQ-CH: CH2 CH-CH OHNHOHNHCH CH-CH CH2 GER-O 2CH5C (I301, CHPCHQ OIL-OH, R

addition was carried out with stirring and cooling and at wherein Rrepresents a member selected from the group a temperature of from to C.During the addition, consisting of hydrogen, chlorine, chloromethyl,chloroa 2,2-dichloro N,N- bis(4 cyclohexylcyclohexyl)ethylethyl, methyl,ethyl and propyl. idenediamine a-isomer product precipitated as acrystalline 30 2. 2,2,3-trichloro N,N'- bis(4 cyclohexylcyclohexyD-solid and was separated by filtration and dried. This butylidenediaminea-isomer. product melted at 9294 C. 3. A process for the preparation ofan N,N'-bis (4-cyclo- In a similar manner, the fi-isomers of2,2,2-trichlorohexylcyclohexyl)alkylidenediarnine having the formulaCHE-43H: /OH,- c G, V /CH,CH: CHz-CH, 0 OH-OH CH,NHCHNH-CH CHC\ /OH,CH7CH: CHr-O 0011-12 GET-CH1 CH7CH:

N,N'-bis(4-cyclohexylcyclohexyl)ethylidenediamine; 2,2 which comprisesthe step of reacting portionwise at least dichloro N,N- bis(4-cyclohexylcyclohexyl)butylideneditwo molecular proportions of(bicyclohexyl)-4-amine with amine; and 2,2-dichloroN,N'-bis(4-cyclohexylcyclohexone molecular proportion of apolychloroaldehyde having yl)pentylidenediarnine may be prepared byreacting (bithe formula cyclohexyl)-4-arnine B-isomer with2,2,2-trichloroacet- 0 aldehyde, 2,2-dichlorobutyraldehyde and2,2-dichlorova- 4? R CC! leraldehyde, respectively. o

The compounds of the present invention have been tested and found to beeffective as herbicides and parasithe Symbol R in the above f lrepresenting a ticides- For Such the Products y dispersed ber selectedfrom the group consisting of hydrogen, chloan inert finly divided Solidand p y as dustsrine, chloromethyl, chloroethyl, methyl, ethyl andpropyl. Also, such mixtures may be dispersed in water with the aid of awetting agent, and the resulting aqueous suspen- N0 references Cited.

1. AN N,N''-BIS(4-CYCLOHEXYLCYCLOHEXYL) ALKYLIDENEDIAMINE HAVING THEFORMULA